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Here, it is first evidenced that 1\u2010methoxy 2\u2010methyl 1\u2010trimethylsilyloxypropene (MTS), i.e., a silyl ketene acetal (SKA)\u2010containing initiator, can be used in presence of the P<jats:sub>4<\/jats:sub>\u2010<jats:italic>t<\/jats:italic>\u2010Bu phosphazene organic base to control the ring\u2010opening polymerization (ROP) of racemic lactide (<jats:italic>rac<\/jats:italic>\u2010LA). The elementary reaction, which rapidly transforms SKA groups into propagating alkoxides, can be leveraged to directly synthesize well\u2010defined poly(methyl methacrylate)\u2010<jats:italic>b<\/jats:italic>\u2010polylactide block copolymers. This is achieved using P<jats:sub>4<\/jats:sub>\u2010<jats:italic>t<\/jats:italic>\u2010Bu as the single organic catalyst and MTS as the initiator for the group transfer polymerization of methyl methacrylate, followed by the ROP of <jats:italic>rac<\/jats:italic>\u2010LA. Both polymerization methods are implemented under selective and controlled\/living conditions at room temperature in THF. This sequential addition strategy further expands the scope of organic catalysis of polymerizations for macromolecular engineering of block copolymers involving propagating species of disparate reactivity.<\/jats:p>","DOI":"10.1002\/marc.202200395","type":"journal-article","created":{"date-parts":[[2022,7,22]],"date-time":"2022-07-22T23:23:55Z","timestamp":1658532235000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Block Copolymer Synthesis by a Sequential Addition Strategy from the Organocatalytic Group Transfer Polymerization of Methyl Methacrylate to the Ring\u2010Opening Polymerization of Lactide"],"prefix":"10.1002","volume":"43","author":[{"given":"Mohamed Samir","family":"Zaky","sequence":"first","affiliation":[{"name":"Laboratoire de Chimie des Polym\u00e8res Organiques (LCPO), UMR 5629 Universit\u00e9 de Bordeaux, INP\u2010ENSCBP  16 av. Pey Berland Pessac Cedex 33607 France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gilles","family":"Guichard","sequence":"additional","affiliation":[{"name":"Univ. Bordeaux, CNRS, CBMN, UMR 5248 Institut Europ\u00e9en de Chimie et Biologie  2 rue Robert Escarpit Pessac F\u201033607 France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8539-4963","authenticated-orcid":false,"given":"Daniel","family":"Taton","sequence":"additional","affiliation":[{"name":"Laboratoire de Chimie des Polym\u00e8res Organiques (LCPO), UMR 5629 Universit\u00e9 de Bordeaux, INP\u2010ENSCBP  16 av. 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